Preparation of Nano Spinel Doped TiO2 and Its Photocatalytic Activity Evaluation Under Visible Light Irradiation.

Nano MgFe-TiO2 photocatalyst was prepared by mixing nanoscale spinel compounds such as magnesium ferrite (MgFe) and TiO2. The cations produced by MgFe are affected by various influencing factors such as calcination temperature, precursor, and mass ratio of Mg and Fe. This study is to evaluate the photocatalytic efficiency of nano MgFe-doped TiO2 under visible light according to the composition ratio of Mg, Fe and TiO2. With an increase the percentage of doping (i.e., Mg and Fe) over TiO2, the band gap between conduction band and valance band decreases, therefore showing better photocatalytic activity in visible light. Also as percentage of doping over TiO2 increases, surface area of the catalyst also increases subsequently resulting in an increase in the adsorption capacity.

Efficient Spent Sulfidic Caustic (SSC) Wastewater Treatment Using Nano TiO2-Bottom Ash (NTB) Composite.

Novel composites with nano-sized TiO2 synthesized on the surface of bottom ash (NTB) were prepared for treatment of spent sulfidic caustic (SSC) wastewater. The efficiency of SSC wastewater treatment was compared and evaluated by using NTBs made with organic binder and inorganic binder, respectively. The treatment efficiency of NTB composite made with organic binder was higher than that of NTB composite made with inorganic binder. Although NBT composite made with inorganic binder had many pores on the surface, the white cement used as binder was excessively applied to the surface, and amount of coated nano-sized TiO2 was decreased. The photocatalytic activity of nano-sized TiO2 is more effective for SSC wastewater treatment than surface adsorption ability of surface pores.

Development of Titanium Dioxide (TiO2)-Embedded Buoyant Photocatalyst Balls Using Expanded Polystyrene.

A new immobilization technique of nanoscale TiO2 powders to expanded polystryrene (EPS) balls with temperature-controlled melting method was developed for mass production, and the characterization of TiO2 powder-embedded EPS (TiEPS) balls was evaluated. Based on the scanning electron microscope (SEM) images and associated energy-dispersive X-ray spectroscopy (EDX) analysis, the components of intact EPS balls are carbon and oxygen whereas those of TiEPS balls are carbon, oxygen, and titanium, indicating that TiO2 powders were embedded on the surface of EPS balls. As also evident by the X-ray diffraction (XRD) and FTIR analyses, no significant changes in crystalline structure of TiO2 powders embedded on the EPS balls were found during the preparation and application processes of TiEPS balls. These characterization results indicated that the patches of TiO2 powders were soundly impregnated over the surface of EPS balls without the significant changes in crystalline structure of TiO2 powders and both structural changes and deformation of EPS polymer.

Application of Titanium Dioxide (TiO2)-Embedded Buoyant Photocatalyst Balls Using Expanded Polystyrene.

A new immobilization technique of nanoscale TiO2 powders to expanded polystryrene (EPS) balls with temperature-controlled melting method was validated for mass production, and the photocatalytic activity of TiO2 powder-embedded EPS (TiEPS) balls using methylene blue (MB) solution with different concentrations under ultraviolet irradiation and under the natural solar light irradiation. Whereas MB molecules were weakly adsorbed onto the surface of both TiO2 powders and supporting polymers without any specific interactions, the photocatalytic efficiency of TiEPS balls with UV (Kapp =0.016~0.043 min-1) was greater through coupled reaction processes (adsorption, photolysis, and photocatalysis). After 5-min sonication, more TiO2 powders on the TiEPS balls can be involved into the both adsorption and photocatalytic reactions of MB, and can increase the MB removal efficiencies. TiEPS balls can be reused for several consecutive runs without any significant decrease in photocatalytic activity until the recalcitrant contaminants were completely coated on the surface of TiEPS balls and loss of TiO2 powders embedded on the surface of TiEPS balls was significant. Based on the aforementioned results, self-floating TiEPS balls manufactured from this simple and cost-effective melting method can be used to remove the organic contaminants and to inhibit the excessive growth of harmful algae in the stagnant water body.

Removal of Humic Acid in Water Using Novel Nanomaterials.

The present study investigates the effectiveness of the photocatalytic degradation of humic acid (HA) in aqueous suspensions. Initial batch scale experiments and tests performed using the Continuous Flow Photoreactor have enabled the close inspection of the performance of the photocatalysts nano TiO2, and nano ZnO dispersions. These photocatalysts were used in aqueous dispersions employing medium-pressure mercury-vapour lamps emitting UV-A (λ = 400 nm) and UV-C (λ = 250 nm). Moreover, glass microfibre filters were embedded and coated with Laponite RD (synthetic polycrystalline swelling clay) in order to produce catalytic films to be used in small scale experiments to remove HA through filtration. The findings of this study shows that the HA adsorb highly onto the ZnO and TiO2 surface thus initiating photodegradation, the effectiveness of which steadily increases with irradiation time along with an increase in the biodegradability of HA.

Preparation of Nanoscale Zinc Oxide-Laponite Composites by Polyvinyl Alcohol Polymerization and Usability for Removal of Trichloroethylene in Water.

Innovative nanoscale ZnO-laponite-polyvinyl alcohol composites (NZLPc) were developed as a valid alternative to nanoscale photocatalysts for mineralization of chlorinated hydrocarbons without difficulties in recovery of nanoscale photocatalyst particles. NZLPc were synthesized by mixing nanoscale ZnO particles with laponite in PVA solution, and by crosslinking PVA solution in the presence of boric acid (≥1.6 M). Different mixing ratios of the raw materials were investigated to develop the stable NZLPc, and X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and transmission electron microscopy characterizations were performed. From the results, a 3:1:1:10 ratio of ZnO, laponite, PVA, and deionized water by weight was appropriate to form spherical NZLPc with high porosities and enhanced mechanical strengths. Also, the degradation efficiencies of trichloroethylene were significantly improved with both NZLPc and UV irradiation, indicating that ZnO-mediated heterogeneous photocatalytic degradation occurred. Thus, the proposed synthesis of NZLPc paves a way for the economical and effective photocatalytic approach to remove the recalcitrant organic compounds in water through the multiple reaction processes (i.e., sorption, photolysis, and photocatalysis).

Algal Growth Potential of Microcystis aeruginosa from Reclaimed Water.

Algal growth potential (AGP) of the cyanobacterium Microcystis aeruginosa (M. aeruginosa, NIES-298) using reclaimed water from various wastewater reclamation pilot plants was investigated to evaluate the feasibility of the reclaimed water usage for recreational purposes. After completing the coagulation and ultrafiltration processes, the concentrations of most contaminants in the reclaimed water were lower than the reuse guidelines for recreational water. However, M. aeruginosa successfully adapted to low levels of soluble reactive phosphorus (PO(3-)(4)) concentrations. The AGP values of M. aeruginosa decreased with the progression of treatment processes, and with the increases in the dilution volume. Also, both the AGP and chlorophyll-a values can be estimated a priori without conducting the AGP tests. Therefore, aquatic ecosystems in locations prone to environmental conditions favorable for the growth of M. aeruginosa require more rigorous nutrient management plans (e.g., reverse osmosis and dilution with clean water resources) to reduce the nutrient availability.

Modeling sorption of neutral organic compound mixtures to simulated aquifer sorbents with pseudocompounds.

The feasibility of the ideal adsorbed solution theory (IAST) in reducing the complexity associated with predicting the sorption behaviors of 12 neutral organic compounds (NOCs) contained in complex mixtures as a fewer number (four to six) of pseudocompounds (groups of compounds) to simulated aquifer sorbents was investigated. All sorption isotherms from individual- and multiple-pseudocompound systems were fit reasonably well ( ≥ 0.953) by the Freundlich sorption model over the range of aqueous concentrations evaluated (i.e., ≤200 µmol L). The presence and magnitude of mutual competition among pseudocompounds varied depending on the composition of the mixtures (i.e., concentrations and polarities of pseudocompounds) and the properties of sorbents (i.e., the fraction of organic carbon and the availability of hydrophilic specific sorption sites). Finally, comparisons between the IAST-based predictions with individual-pseudocompound sorption parameters and experimentally measured data revealed that the accuracy in predicting the sorption behaviors of several NOCs in terms of a fewer number of pseudocompounds decreased with increasing deviations from the assumption of equal and ideal competition in the IAST (i.e., differential availability of sorption sites and nonideal competitions among pseudocompounds).

Modelling heavy-metal phytoextraction capacities of Helianthus annuus L. and Brassica napus L.

Greenhouse experiments were conducted to test the phytoextraction potential of sunflower (Helianthus annuus L.) and rape (Brassica napus L.) during the initial growth in the heavy metal (i.e., Cd, Ni, Zn, and Pb) contaminated soil. The target plants were grown for 30 d in pots filled up with soil treated with various concentrations of heavy metals. The wet/dry weights of plants and heavy-metal concentrations were measured, and the bioaccumulation factors (BAFs) and Freundlich-type uptake model were then used to measure their capacities of phytoextracting accumulated heavy metals from the soil. It was observed that the wet/dry weights of sunflower and rapeseed decreased, and heavy-metal mass uptake increased in plants commensurate with the elevating heavy metal concentrations in the soil. The sunflower BAF for heavy metals was higher than that of rapeseed. The Freundlich-type uptake model suitably described the phytoextraction capacities of sunflower and rapeseed in a soil contaminated with a single heavy metal and can be used to compare the phytoextraction capacities of different plants for the same heavy metal or of the same plant with different heavy metals. Although this study is based on limited data from two species of plants and soils contaminated with one heavy metal, it provides a basis for evaluating the ability of plants to accumulate heavy metals during their initial growth stages. Additional studies utilizing diverse hyperaccumulator plants and soils polluted with multiple heavy metals are essential to enhance the suitability of the Freundlich-type uptake model for assessing the phytoextraction capacities of intricate systems.

Evaluation of the lead and chromium removal capabilities of Bacillus subtilis-induced food waste compost-based biomedia.

Food waste compost (FWC) is a sustainable recycling approach employed in soil media, offering extensive advantages to urban areas by promoting resource circulation and effectively managing water pollution. To improve value, Bacillus subtilis (B. subtilis)-induced FWC-based biomedia (BIBMFWCs) was produced via a secondary treatment involving selective meso-thermophilic stages. During the production of BIBMFWCs, physicochemical properties were found to have favorable characteristics for the efficient removal of metal ions. The produced organic-carbonate complex structure demonstrated the synergistic effect involving simultaneous sorption/precipitation mechanisms for the removal of Pb(II) and Cr(III). Also, the dose of B. subtilis has an impact on the pseudo-second-order (PSO) and intra-particle diffusion (IPD) reaction, leading to distinct removal capacities for Pb(II) and Cr(III) [24.26-24.74 mg g-1 in Pb(II) and 12.7-23.93 mg g-1 in Cr(III)]. Furthermore, B. subtilis, an inducing mediator for microbial metabolites, exhibits the potential to facilitate the removal of Pb(II) and Cr(III) through biological modification of raw materials, which are transformed, facilitating the presence of hydroxyl groups, immobilizing metal ions, and enabling ion exchange via biogenic carbonate formation processes. Finally, the developed BIBMFWCs could be used as a nature-based solution (NBS) material without in-situ pH control.

Sorption of nonpolar neutral organic compounds to low-surface-area metal (hydr)oxide- and humic acid- coated model aquifer sands.

The roles of mineral-bound humic acid (HA) and mineral surfaces in the sorption of six nonpolar neutral organic compounds with relatively high aqueous solubility, S(w), (1,2,4-trichlorobenzene, 1,4-dichlorobenzene, chlorobenzene, m-xylene, toluene, and benzene) to low-surface-area (i.e., ≤ 1.2 m(2)/g) metal (hydr)oxide- and HA-coated sands with low organic carbon fractions (i.e., 0.006% ≤ f(oc) ≤ 0.044%) were investigated using well-characterized mineral surfaces [i.e., α-FeO(OH)- or Al(2)O(3)- coated sands], terrestrial HA, and solutions with relatively constant pH and ionic strength. Sorption isotherms of all six compounds to low-surface-area metal (hydr)oxide-and HA-coated sands were practically linear (i.e., 0.898 ≤ n ≤ 1.06), and resulted from a combination of sorption to both mineral-bound HA and mineral surfaces, with the dominance of either contribution depending on the properties of the sorbents (e.g., f(oc)) and organic compounds (e.g., S(w) and K(ow)). Compared to HA-associated high-surface-area, pure metal (hydr)oxides or clay minerals illustrating that loading levels of HA significantly impacted sorption affinity (i.e., K(oc)) and linearity (i.e., n) for particularly hydrophobic compounds (i.e., phenanthrene, anthracene and pyrene) due to the changes in fractionation, and structural and chemical properties of mineral-bound HA, the subsequent changes of sorption affinity and linearity appeared to be insignificant for the sorption of organic compounds with relatively high S(w) to low-surface-area metal (hydr)oxide- and HA-coated sands with low f(oc) values. Thus, the predictive models for the sorption of organic compounds with relatively high S(w) to low-surface-area metal (hydr)oxide- and HA-coated sands may not be remarkably improved by incorporating the complex changes of sorption affinity and linearity caused by the changes in fractionation, and structural and chemical properties of mineral-bound HA, although the mineral surfaces apparently caused physical and chemical changes of HA, and vice versa during adsorption onto mineral surfaces.

Application of WQIEUT and TSIKO for comprehensive water quality assessment immediately after the construction of the Yeongju Multipurpose Dam in the Naeseong Stream Basin, Republic of Korea.

This study evaluated changes in the aquatic environment and river water quality due to the construction of the Yeongju Multipurpose Dam (YMD) in the Naeseong Stream Basin, Republic of Korea, over eight years. This study evaluated water quality characteristics immediately after dam construction in the target area with aquatic environmental values and important water quality parameters using classification schemes. The drastic formation of new lentic systems in the upstream dammed pool presented exponential algal growth and high potential availability of nitrogenous compounds depending on seasonally. The results of the river system analyzed with the water quality index focused on eutrophication (WQIEUT) and trophic state index of the Republic of Korea (TSIKO) provided adequate complementary information for specific water quality background within the extensive basin for future management. From the results, inflow and accumulation of anthropogenic organic matter as potential eutrophic factors in the upstream dammed pool were significant in the short-term period. However, the downstream lotic systems adjacent to the dam presented the temporary disturbance by physical factors. Furthermore, potential microbial factors were significant in the outlet in the basin depending on seasonally. These results using classification schemes can aid accessible decision-making for water quality management to prevent eutrophication in the dammed pool of upstream or best management practices (BMP) with microbial source tracking (MST) approaches in the downstream area.

Physicochemical and fertility characteristics of microalgal soil ameliorants using harvested cyanobacterial microalgal sludge from a freshwater ecosystem, Republic of Korea.

The recovery and reuse strategy of cyanobacterial microalgal sludge (CyanoMS) is a novel sustainable platform that can mitigate cyanobacterial harmful algal blooms (CyanoHABs) in the freshwater system. This study aimed to assess the nutritional feasibility of harvested CyanoMS for microalgal soil ameliorants (MSAs) as efficient biofertilizers by the composting process. Most MSAs exhibited stable nutrient levels during the sequential metabolic phases for the entire period. The qualitative value of all MSAs using CyanoMS as a biofertilizer was verified by the excellent Fertility Index (FI), Clean Index (CI), and plant growth values. Also, successfully matured MSAs provided long-term support for retarded release of nutrients along the microbial transitional pathway. However, suitable CyanoMS contents of 11.7-37.6% (w/w) in MSAs were critical for efficient microbial activation and substrate inhibition. Since these results were fundamentally based on microbial transition on the CyanoMS content, optimum weight content and composting period were required. Nevertheless, MSAs were commercially applicable to high value-added crops due to their high fertilization potential and recyclable value.

Sorption of nonpolar neutral organic compounds to model aquifer sands: implications on blocking effect.

The use of a calibrated two-component model with a single blocking parameter for both adsorption onto mineral surfaces and partitioning into soil organic matter of two nonpolar sorbates (i.e., 1,2,4-trichlorobenzene and benzene) was evaluated by using several humic acid (HA)-coated sands with different fractions of organic carbon (f(oc)) ranging from 0.006 to 0.154%. Sorption of nonpolar sorbates to both untreated and heated sands was nearly linear due to the reduction of heterogeneous adsorption potential by strongly adsorbed vicinal water molecules over hydrophilic mineral surfaces. Sorption of nonpolar sorbates to the HA-coated sands was also essentially linear, and resulted from a combination of adsorption onto mineral surfaces and partitioning into soil organic matter, with the dominance of either contribution depending on the properties of the sorbents (e.g., f(oc)) and the sorbates (e.g., K(ow)). Contrary to the previous studies suggesting that surface area is the only variable affecting the magnitude of the adsorption coefficient onto modified high-surface-area clay minerals, the difference in adsorptive affinity of nonpolar sorbates onto modified mineral surfaces (i.e., K(S,c)) relative to that for pure mineral surfaces (i.e., K(S)) also may be important for low-surface-area, coarse-grained model aquifer sands. However, the improvement in predicted sorption behavior by incorporating the blocking effect is insignificant for low-surface-area, coarse-grained model aquifer sands.

Evaluation of heavy metal phytotoxicity to Helianthus annuus L. using seedling vigor index-soil model.

A mathematical model to estimate seedling vigor index (SVI) of sunflower (Helianthus annuus L.) seeds in soils contaminated with heavy metals was developed. This model was used to quantitatively describe the complex effects of heavy metal concentrations in soils (Cs) on seed germination and seedling growth. Negative linear regressions between relative seed germination percentage (GP), root length (Lr), and shoot length (Ls) versus log Cs varied as a function of soil properties and type and concentration of heavy metals. With an increase in the heavy metal concentration in soils, the predicted SVI values decreased and reasonably described the experimental SVI values within an 80% prediction band. This demonstrates that SVI values can be predicted, a priori, using SVI-soil models. Based on the sensitivity analysis, root elongation was more significantly affected by the external environment than shoot elongation. Consequently, the SVI-soil model developed in this study can explain heavy metal phytotoxicity to sunflower in complex soil systems. Further research using a diverse range of hyperaccumulator plants and soils is required to render SVI-soil model more available for complex systems in predictions of heavy metal phytotoxicity and hyperaccumulating behaviors of hyperaccumulator plants in various soil systems.

Generation of Nano Bubbles Using Cavitation Technique and Monitoring of Strawberry Growth by the Generated Nano Bubbles.

In this study, nano bubbles (NBs) of around 100 nm size were generated by using GoodSam-NB generator (made by S company) which utilizes cavitation technique. The generated NBs were directly applied to the strawberry cultivation process to monitor the productivity of strawberry. When the aqueous nutrient solution with NBs was supplied to the strawberry culture medium, it had a slightly higher initial concentration of dissolved oxygen (DO) compared to the nutrient solution prepared with ordinary groundwater at a concentration of about 9 mg/L and did not decrease over time. In other words, NBs helped to supply DO to support the development of roots in the early stage of strawberry's growth, thereby promoting the overall growth of strawberries. After feeding the NBs nutrient solution, the nitrate concentration of the discharged solution was analyzed. The concentration of the nitrate in the effluent was reduced, hence the growth of strawberry was promoted. It can be concluded that the DO contained in aqueous nutrient solution with NBs helped the nitrate to be smoothly taken from the soil.

Evaluation of Titanium Tetrachloride (TiCl4) as an Alternative Coagulant and Characterization of Recovered TiO2.

Titanium tetrachloride (TiCl4) as an alternative coagulant to remove organic matters and nutrients from the effluent of the secondary wastewater treatment was evaluated by comparison of removal efficiency of total phosphorous to Al- and Fe-based coagulants. Also, the surface characteristics, elemental contents, and crystallinity of the TiO2 produced from wastewater sludge flocculated with TiCl4 coagulant were investigated depending on the calcination temperatures. The more dosages of coagulants were injected, the greater concentrations of the cations (Al+3, Fe+3, Ti+4) and hydrogen ions (H+) resulted in the lower pH. Also, TiCl4 formed larger and heavier flocs than other coagulants and resulted in greater T-P removal efficiencies with reduced amounts of dosage. The phase change of anatase and rutile crystalline structures of TiO2 incinerated from wastewater sludges of TiCl4 coagulant was observed at relatively high calcination temperatures due to the existence of mixtures of organic matters, nutrients, and various impurities in the wastewater sludges of TiCl4 coagulant. Both C and P atoms were found to be mainly doped in/on TiO2 and the C and P atom originated from residual carbon of the settled organic matters and phosphorus nutrients present in effluents from sewage treatment plant, respectively. Therefore, 600-800 °C is the optimal calcination temperatures for TiO2 produced from TiCl4 coagulant flocculated with effluents from sewage treatment plant.

Electromagnetically-vibrated solid-phase microextraction for analysis of aqueous-miscible organic compound transport in soil columns.

Current methods of sampling pore water from soil columns to determine solute concentrations are slow and require relatively large volumes. Accordingly, an electromagnetically-vibrated (EMV) solid-phase microextraction (SPME) device was evaluated for determining temporal and spatial distributions of solute pore-water concentrations (solute concentration profiles) for four organic compounds, two polar (2-hexanone, 2,4-dimethyl phenol) and two nonpolar (toluene, 1,4-dichlorobenzene), in columns packed with simulated aquifer sands with different fractions of organic carbon. In batch equilibrium extraction tests, the equilibrium extraction time of the organic compounds in aqueous mixtures decreased from 30 to less than 10 min as the frequency of electromagnetic vibration increased from zero to 250 Hz. Mixture effects were not statistically significant (p > 0.05) in the extraction process using EMV SPME. Comparisons of the solute concentration profiles within the soil columns at different elapsed times measured by pore-water samples and in situ EMV SPME extractions revealed both methods were equally effective. However, EMV SPME extraction removed no solution volume and only 0.6-14% of the solute mass removed by the pore-water sample collections, substantially minimizing disturbances to solute transport and fate. Thus, the equilibrium extraction-based calibration method using EMV SPME offers an effective approach for rapidly and accurately determining solute concentration profiles in column tests with negligible solute mass loss and minimal solution flow disturbance.

Comparison of Immobilization Methods for TiO2-Embedded Expanded Polystyrene Balls and Growth Inhibition of Microcystis aeruginosa.

Two immobilization methods (i.e., ice water-soaked using a digital temperature controller vs. freeze-dried using liquid nitrogen) were applied for mass production techniques of TiO2-embedded expanded polystyrene (TiEPS) balls with nanoscale TiO2 particles embedded on EPS balls. No significant changes in crystalline structure of TiO2 nanoparticles embedded on the TiEPS balls were observed during the mass production of TiEPS balls. Greater residuals of freeze-dried TiEPS balls suggested the improved immobilization methods for mass production procedures of TiEPS balls. Although similar growth inhibition between TiEPS balls using two immobilization methods was observed within 10 hrs, both growth and reproduction of M. aeruginosa can be more significantly inhibited by applying the freeze-dried TiEPS balls after 10 hrs. These results were mainly attributed to the difference in exposed surface area of embedded TiO2 nanoparticles which generated various reactive oxygen species peroxidizing and leading to the inactivation and degradation of M. aeruginosa. Relatively greater k value (0.207 day-1) was estimated from freeze-dried TiEPS balls than that (0.089 day-1) from ice water-soaked TiEPS balls, suggesting that both growth and reproduction of M. aeruginosa were effectively inhibited with greater amounts of reactive oxygen species generated from freeze-dried TiEPS balls. Consequently, self-floating freeze-dried TiEPS balls can be readily applied to inhibit the excessive growth of harmful algae in the stagnant water body without the recovery process for long time.

Removal of Cesium in Water Using Novel Composites Synthesized Nano-Sized Prussian Blue with Carbonyl Iron.

Among the various radioactive materials, Cesium is a major source of radioactive contamination and known to be the most dangerous radioactive material, can cause enormous damage to the ecosystem environment when released into the environment. Prussian Blue (PB) has been used as an adsorbent to effectively remove cesium, however it has the problem of being difficult to separate in water. In this study, carbonyl iron (CI) which is known as ferromagnetic synthesized with precursor of PB (FeCl3 and potassium ferricyanide) to solve the problem of PB particles. Adsorption isotherm experiments were also conducted to evaluate the cesium removal ability of the manufactured novel composites. The results obtained in the present study indicate that the novel composite has a cesium removal rate of 99.88% and a distribution coefficient value of 124,900 mL/g. Adsorption behavior follows Langmuir isotherms and the maximum adsorption amount is (qm) 79.3 mg/g. In conclusion, Nano-sized Prussian blue with carbonyl Iron prepared through this study has excellent cesium removal capacity, and it can be completely separated from water when used directly in the cesium treatment field.